Ceramic laminate and method of manufacturing ceramic sintered body

ABSTRACT

There are provided a method of manufacturing a ceramic sintered body. A method of manufacturing a ceramic sintered body according to one aspect of the invention may include: preparing at least one ceramic sheet having first ceramic particles and glass particles; preparing at least one constraining sheet having second ceramic particles having a smaller particle size than the glass particles and the first ceramic particles; forming a ceramic laminate by alternating the ceramic sheet and the constraining sheet while the ceramic sheet and the constraining sheet are in contact with each other; and sintering the ceramic laminate so that components, which do not react with the first ceramic particles, from the glass particle are moved into the constraining sheet to sinter the constraining sheet when the ceramic sheet is sintered.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.12/510,162, filed on Jul. 27, 2009, which claims the priority of KoreanPatent Application No. 10-2008-0104468, filed on Oct. 23, 2008, andKorean Patent Application No. 10-2009-0045995, filed on May 26, 2009, inthe Korean Intellectual Property Office, the disclosure of all of whichis incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a ceramic laminate and a method ofmanufacturing a ceramic sintered body.

2. Description of the Related Art

In general, multilayer ceramic substrates have been used as componentson which active elements, such as semiconductor IC chips, and passiveelements, such as capacitors, inductors and resistors, are mounted.Also, multilayer ceramic substrates have simply been used insemiconductor IC packages. Specifically, these multilayer ceramicsubstrates have been widely used to construct various electroniccomponents including PA module substrates, RF diode switches, filters,chip antennas, various package components and complex devices.

In order to manufacture the above-described multilayer ceramicsubstrates, dielectric sheets having wiring conductors formed thereonare laminated, and the sintering process is necessarily performed on thelaminate to achieve optimum characteristics. However, after thissintering process is performed, the multilayer ceramic substrates shrinkbecause ceramics are sintered. Since multilayer ceramic substrates donot shrink evenly in all directions, dimensional changes occur in theplanar direction of ceramic layers. The shrinkage of the ceramicsubstrate in the planar direction also causes undesirable deformationsor distortions. Specifically, the accuracy of external electrodes forconnections with chip components, which are mounted onto multilayerceramic substrates, may be reduced or wiring conductors may bedisconnected.

The shrinkage of the ceramic substrate in the planar direction causes amisalignment between conductor patterns and the ceramic substrate whenmounting components. As a result, it may be impossible to mountsemiconductor chips, such as chip size packages (CSPs) and MCM(multi-chip modules), with high accuracy. Therefore, there has beenproposed a so-called non-shrinking method in order to remove shrinkagein the planar direction in a sintering process when multilayer ceramicsubstrates are manufactured.

According to a general non-shrinking method, constraining sheets areformed using alumina powder, which is a ceramic that is not sintered at900° C. or less, the formed constraining sheets are laminated on the topand bottom of low temperature co-fired ceramic (LTCC) dielectric sheetsto form a ceramic substrate, a predetermined weight is applied to theceramic substrate to perform plasticizing and sintering, and then theconstraining sheets are removed therefrom, thereby obtaining a ceramicsubstrate. FIG. 1 is a cross-sectional view illustrating one process ofa general non-shrinking method of manufacturing a ceramic substrate.Constraining layers 11 are disposed on the top and bottom of a ceramiclaminate 10 that has a plurality of ceramic sheets laminated onto oneanother. Here, each of the constraining layers 11 is not sintered at asintering temperature of the ceramic laminate 10. The constraininglayers 11 can prevent shrinkage in the planar direction of the ceramiclaminate 10 during the sintering process.

However, in the non-shrinking method, illustrated in FIG. 1, a largeconstraining force is applied to ceramic sheets adjacent to theconstraining sheets 11, but a relatively small constraining force isapplied to the inner part of the ceramic laminate 10. Since theconstraining force is unevenly applied to the ceramic laminate 10, astress imbalance occurs in the inner part of the ceramic laminate 10. Asa result, the reliability of the ceramic substrate may be deteriorated.This problem may be worsened when the ceramic laminate 10 is thick.

SUMMARY OF THE INVENTION

An aspect of the present invention provides a ceramic laminate havingconstraining layers that can evenly exert a constraining force onto aceramic laminate during sintering.

Another aspect of the present invention provides a method ofmanufacturing a ceramic sintered body that is obtained by sintering theceramic laminate.

According to an aspect of the present invention, there is provided aceramic laminate including: at least one ceramic sheet having firstceramic particles and glass particles; and at least one constrainingsheet having second ceramic particles and alternating with the ceramicsheet while the constraining sheet and the ceramic sheet are in contactwith each other, wherein the glass particles and the first ceramicparticles each have a larger particle size than the second ceramicparticles, and the first ceramic particles have a particle size of 1 μmor more, the glass particles have a particle size within the range of 1μm to 10 μm, and the second ceramic particles have a particle size of 1μm or less.

The ceramic sheet and the constraining sheet may each include aconductive pattern and a conductive via.

The ceramic sheet may have a thickness within the range of 20 μm to 200μm.

The constraining sheet may have a thickness of 20 μm or less.

The ceramic sheet may be thicker than the constraining sheet.

The first and second ceramic particles may be formed of the samematerial.

The constraining sheet may include the second ceramic particles andorganic binders.

The glass particles may include a composition represented by (Ca, Sr,Ba)O—Al₂O₃—SiO₂—ZnO—B₂O₃.

The first ceramic particles may include Al₂O₃.

The ceramic sheet may include 40 to 80 wt % of the glass particles and20 to 60 wt % of the first ceramic particles.

The glass particles include 2 to 10 wt % of ZnO.

According to another aspect of the present invention, there is provideda method of manufacturing a ceramic sintered body, the method including:preparing at least one ceramic sheet having first ceramic particles andglass particles; preparing at least one constraining sheet having secondceramic particles having a smaller particle size than the glassparticles and the first ceramic particles; forming a ceramic laminate byalternating the ceramic sheet and the constraining sheet while theceramic sheet and the constraining sheet are in contact with each other;and sintering the ceramic laminate so that components, which do notreact with the first ceramic particles, from the glass particle aremoved into the constraining sheet to sinter the constraining sheet whenthe ceramic sheet is sintered.

The constraining sheet may be sintered after the ceramic sheet issintered.

The constraining sheet may be sintered at the sintering temperature ofthe ceramic sheet.

The glass particles may include a composition represented by (Ca, Sr,Ba)O—Al₂O₃—SiO₂—ZnO—B₂O₃.

The first ceramic particles may include Al₂O₃.

The ceramic sheet may include 40 to 80 wt % of the glass particles and20 to 60 wt % of the first ceramic particles.

The glass particles may include 2 to 10 wt % of ZnO.

Components, which do not react with the first ceramic particles, mayinclude ZnO.

The first ceramic particles may have a particle size of 1 μm or more,the glass particles may have a particle size within the range of 1 μm to10 μM, and the second ceramic particles may have a particle size of 1 μmor less.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects, features and other advantages of thepresent invention will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings, in which:

FIG. 1 is a cross-sectional view illustrating one process of a generalnon-shrinking method of manufacturing a ceramic substrate;

FIG. 2 is a cross-sectional view illustrating a ceramic laminateaccording to an exemplary embodiment of the invention;

FIG. 3 is a detailed view illustrating a ceramic sheet and aconstraining sheet of the ceramic laminate, shown in FIG. 2;

FIG. 4 is an enlarged view illustrating particles constituting a ceramicsheet and a constraining sheet; and

FIG. 5 is an enlarged view illustrating particles constituting a ceramicsheet and a constraining sheet.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Exemplary embodiments of the present invention will now be described indetail with reference to the accompanying drawings. The invention mayhowever be embodied in many different forms and should not be construedas limited to the embodiments set forth herein. Rather, theseembodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the invention to thoseskilled in the art. In the drawings, the shapes and dimensions may beexaggerated for clarity, and the same reference numerals will be usedthroughout to designate the same or like components.

FIG. 2 is a cross-sectional view illustrating a ceramic laminateaccording to an exemplary embodiment of the invention. FIG. 3 is adetailed view illustrating a ceramic sheet and a constraining sheet ofthe ceramic laminate, shown in FIG. 2. First, referring to FIG. 2, aceramic laminate 100 according to this embodiment includes ceramicsheets 101 and constraining sheets 102. The ceramic sheets 101 and theconstraining sheets 102 alternate with each other while they are bondedto each other. The ceramic sheets 101 may be formed using glass, ceramicfillers and organic binders by the doctor blade method known in therelated art. The constraining sheets 102 include glass ceramic fillersand organic binders and a very small amount of glass so that theconstraining sheets 102 cannot be sintered at the sintering temperatureof the ceramic sheets 101. These constraining sheets 102 can exert aconstraining force onto the ceramic sheets 101 during sintering.

As described above, unlike the related art, in the ceramic laminate 100,each of the constraining sheets 102 is disposed between the ceramicsheets 101. The constraining sheets 102 remain in the final device, thatis, a ceramic sintered body. To this end, as shown in FIG. 3, conductivepatterns 103 and conductive vias 104 may be provided in the ceramicsheets 101 and the constraining sheets 102.

As the constraining sheets 102 are in contact with the top and bottom ofeach of the ceramic sheets 101, the constraining force can be evenlyexerted onto the ceramic sheets 101 to thereby prevent a stressimbalance. Furthermore, since the constraining sheets 102 do not need tobe removed after the sintering process, processing convenience can besignificantly increased. As it will be described below, even thoughglass particles are moved within the constraining sheets 102 during thesintering process, an excessive volume of the constraining sheets 102having a high proportion of ceramic fillers may deteriorate propertiesof a ceramic sintered body after the sintering process, that is, aceramic substrate. Therefore, the above-described constraining sheet mayhave a thickness t2 of 20 μm or less, preferably, 10 μm or less. Theceramic sheet 101 has a thickness t1 within the range of 20 μm to 200μm.

As described above, the constraining sheets 102 include ceramic fillersthat are not sintered at the sintering temperature of the ceramic sheets101. However, as the ceramic sheets 101 start to be sintered, theconstraining sheets 102 may also be sintered at a relatively lowtemperature. This will be described with reference to FIGS. 4 and 5.FIGS. 4 and 5 are views enlarging particles constituting a ceramic sheetand a constraining sheet. Here, in FIG. 4, the ceramic laminate 100,shown in FIG. 2, is kept at a temperature less than the sinteringtemperature, and in FIG. 5, glass particles are being moved during thesintering process. During the sintering process of the ceramic sheets101, when the constraining sheets 102 are not sintered, and then startto be sintered at a temperature much higher than the sinteringtemperature of the ceramic sheets 101, the sintering state of theceramic sheets 101, which have already been sintered, may bedeteriorated. Considering this, in this embodiment, glass particles aremoved into the constraining sheets 102 while the ceramic sheets 101 aresintered.

If glass particles G, partially constituting the ceramic sheets 101, aremoved into the constraining sheets 102 during the sintering process, thesintering temperature of the constraining sheets 102 is graduallyreduced, and thus the constraining sheets 102 may be sintered at atemperature close to the sintering temperature of the ceramic sheets101. Therefore, the ceramic sintered body can be obtained in which theceramic laminate 100 is evenly sintered. To this end, a diameter D1 ofeach of the glass particles G and a diameter D3 of each of the ceramicparticles (first ceramic particles C1) constituting the ceramic fillersthat are included in the ceramic sheets 101 need to be larger than adiameter D2 of each of the ceramic particles (second ceramic particlesC2) that are included in the constraining sheets 102. As shown in FIG.5, this helps to promote the movement of the glass particles G bycapillary action. Specifically, the particle diameter D1 of each of theglass particles G may be within the range of 1 μm to 10 μm, preferably,around 2.5 μm. The first ceramic particles C1 may be of similar size tothe glass particles G in terms of sintering characteristics. Preferably,the particle diameter D3 of the ceramic particle may be 1 μm or more.Considering this, the particle diameter D2 of the second ceramicparticle C2 may be 1 μm. Here, since the plurality of glass particles Gand the first and second ceramic particles C1 and C2 exist, the particlediameter can be defined as a mean particle diameter.

Since the glass penetrates into the constraining sheets 102 during thesintering process, the second ceramic particles C2, included in theconstraining sheets 102, are preferably formed of a material that hasrelatively higher wettability with respect to the glass of the ceramicsheets 101. The same applies to the first ceramic particles C1. Whenunreacted glass materials remain among the glass particles G during thesintering process, these unreacted glass materials may be easily movedinto the constraining sheets 102. Considering these factors, the glassparticles G may be formed of a composition represented by (Ca, Sr,Ba)O—Al₂O₃—SiO₂—ZnO—B₂O₃, and the first ceramic particles C1 may beformed of Al₂O₃. Here, the glass particles G and the first ceramicparticles C1 are mixed while the glass particles G are added at a ratioof 40 to 80 wt % of (Ca, Sr, Ba)O—Al₂O₃—SiO₂ and the first ceramicparticles C1 are added at a ratio of 20 to 60 wt % of Al₂O₃ with respectto the ceramic sheets 101.

During the sintering process, glass, containing large amounts of Zn andB, is introduced into the constraining sheets 102 from the ceramicsheets 101. Here, as described, the glass, introduced into theconstraining sheets 102, is left without making a reaction to the firstceramic particles C1. The glass, introduced into the constraining sheets102, results in a pore-free interface between the ceramic sheets 101 andthe constraining sheets 102. Specifically, during the sintering process,when (Ca, Sr, Ba)O—Al₂O₃—SiO₂-based glass reacts with Al₂O₃, (Ca, Sr,Ba)Al₂Si₂O₈, unreacted glass components are obtained. In the abovereaction, ZnO mostly becomes unreacted glass components. Here, a crystalof (Ca, Sr, Ba)Al₂Si₂O₈ rarely contains ZnO. Crystallographically, sincean ionic radius of each of the elements, such as Ca, Sr and Ba, is muchlarger than that of Zn, Zn is difficult to substitute for the elements.Therefore, the glass components containing large amounts of Zn are movedinto the constraining sheets 102 during the sinter process of theceramic sheets 101. That is, glass particles G′, having moved to theconstraining sheets 102, shown in FIG. 5, are different from the glassparticles G that have existed in the ceramic sheets 101.

The glass components containing the large amounts of Zn, having movedinto the constraining sheet 102, react with the second ceramic particlesC2, for example, Al₂O₃, a crystalline phase, such as ZnAl₂O₄, isprecipitated. As this reaction occurs, the unreacted glass in theceramic sheet 101 is introduced into the constraining sheet 102 at ahigher rate. Herein, the constraining sheets 102 are sintered. When ZnOis added to the (Ca, Sr, Ba)O—Al₂O₃—SiO₂-based glass, the content of ZnOneeds to be appropriately controlled. For example, SiO₂ is added at aratio of 40 to 70 wt %, Al₂O₃ is added at a ratio of 5 to 20 wt %, (Ca,Sr, Ba)O is added at a ratio of 10 to 35 wt %, Ba₂O₃ is added at a ratioof 5 to 15 wt %, ZnO is added at a ratio of 2 to 10 wt % by weight ofthe glass particles G. When the ZnO content is 2 wt % or higher, thisensures high fluidity of the glass of the ceramic sheet 101, and thus,the remaining space of the ceramic sheets 101 after glass is introducedinto the constraining sheets 102 can be filled with the glass. However,when the amount of ZnO increases considerably, basic properties of theLTCC materials, including strength, chemical resistance and insulation,may be adversely affected. Therefore, the content of ZnO does notpreferably exceed 10 wt %.

The inventors of this invention have carried out experiments undervarious conditions to find out the effects of the invention. That is,the inventors sintered ceramic laminates and measured contractionratios, and the results are shown in Table 1 as follows.

TABLE 1 Constraining Ceramic sheet layer Particle Particle FractionParticle Sintering Contraction thickness size (G) size (C1) size (C1)thickness (C2) temperature ratio 1 50 μm 2.5 μm 1.7 μm 35 wt % 6.5 μm600 nm 850° C. 0.342 2 50 μm 2.5 μm 1.7 μm 35 wt % 6.5 μm 600 nm 870° C.0.258 3 50 μm 2.5 μm 1.7 μm 35 wt % 6.5 μm 600 nm 900° C. 0.183 4 100 μm2.5 μm 1.7 μm 50 wt % 6.5 μm 600 nm 850° C. 0.500 5 100 μm 2.5 μm 1.7 μm50 wt % 6.5 μm 600 nm 870° C. 0.458 6 100 μm 2.5 μm 1.7 μm 50 wt % 6.5μm 600 nm 900° C. 0.183 7  50 μm 2.5 μm 2.5 μm 40 wt % 6.5 μm 600 nm850° C. 0.658 8  50 μm 2.5 μm 2.5 μm 40 wt % 6.5 μm 600 nm 870° C. 0.4839  50 μm 2.5 μm 2.5 μm 40 wt % 6.5 μm 600 nm 900° C. 0.617 10  50 μm 4.5μm 1.7 μm 30 wt % 4.5 μm 600 nm 870° C. 0.370 11  50 μm 2.5 μm 1.7 μm 50wt % 4.5 μm 600 nm 870° C. 0.605 12 100 μm 2.5 μm 1.7 μm 50 wt % 4.5 μm600 nm 870° C. 0.674 13 100 μm 2.5 μm 1.7 μm 40 wt % 4.5 μm 600 nm 870°C. 0.277 14 100 μm 2.5 μm 1.7 μm 30 wt % 4.5 μm 600 nm 870° C. 0.342 15100 μm 2.5 μm 1.7 μm 40 wt % 5.5 μm 500 nm 870° C. 0.340 16 100 μm 2.5μm 1.7 μm 30 wt % 5.5 μm 500 nm 870° C. 0.407

Sample Nos. 1 to 3 are glass for ceramic sheets, which is formed ofCa—Al—Si—O glass. Sample Nos. 4 to 6 and 11 to 16 are formed ofCa—Al—Si—Zn—O glass. Sample Nos. 7 to 9 are formed of Mg—Ca—Si—O glass.Sample No. 10 is formed of Ca—Al—Si—B glass.

As described above, when a non-shrinking method according to theembodiments of the invention is used, a constraining force is evenlyexerted onto a ceramic laminate, and constraining sheets are naturallysintered at a temperature around the sintering temperature of ceramicsheets because of the transferral of glass particles to thereby increasesintering characteristics.

As set forth above, according to exemplary embodiments of the invention,a ceramic laminate having constraining sheets that can evenly exert aconstraining force onto a ceramic substrate during sintering can beprovided. Further, a non-shrinking method according to exemplaryembodiments of the invention allows constraining sheets to be naturallysintered at a temperature around the sintering temperature of ceramicsheets because of the transferral of glass particles to thereby increasesintering characteristics. Furthermore, since there is no need to removeconstraining sheets after sintering, processing convenience can besignificantly increased.

While the present invention has been shown and described in connectionwith the exemplary embodiments, it will be apparent to those skilled inthe art that modifications and variations can be made without departingfrom the spirit and scope of the invention as defined by the appendedclaims.

What is claimed is:
 1. A method of manufacturing a ceramic sinteredbody, the method comprising: preparing at least one ceramic sheet havingfirst ceramic particles and glass particles; preparing at least oneconstraining sheet having second ceramic particles having a smallerparticle size than the glass particles and the first ceramic particles;and forming a ceramic laminate by alternating the ceramic sheet and theconstraining sheet while the ceramic sheet and the constraining sheetare in contact with each other, wherein the glass particles comprise acomposition represented by (Ca, Sr, Ba)O—Al₂O₃—SiO₂—ZnO-B₂O₃, whereinthe ceramic sheet comprises 40 to 80 wt % of the glass particles and 20to 60 wt % of the first ceramic particles, wherein the 40 to 80 wt % ofthe glass particles comprise 2 to 10 wt % of ZnO, wherein theconstraining sheet does not contain glass particles, wherein the methodfurther comprises: sintering the ceramic laminate so that ZnO, whichdoes not react with the first ceramic particles, from the glassparticles is moved into the constraining sheet to allow the constrainingsheet to be sintered while the ceramic sheet is sintered.
 2. The methodof claim 1, wherein the sintering temperature of the constraining sheetis about the same as the sintering temperature of the ceramic sheet. 3.The method of claim 1, wherein the first ceramic particles compriseAl₂O₃.
 4. The method of claim 1, wherein the first ceramic particleshave a particle size of 1 μm or more, the glass particles have aparticle size within the range of 1 μm to 10 μm, and the second ceramicparticles have a particle size of 1 μm or less.
 5. The method of claim1, wherein the ceramic sheet and the constraining sheet each comprises aconductive pattern and a conductive via.
 6. The method of claim 1,wherein the ceramic sheet has a thickness within the range of 20 μm to200 μm.
 7. The method of claim 1, wherein the constraining sheet has athickness of 20 μm or less.
 8. The method of claim 1, wherein theceramic sheet is thicker than the constraining sheet.
 9. The method ofclaim 1, wherein the first and second ceramic particles are formed ofthe same material.
 10. The method of claim 1, wherein the constrainingsheet comprises the second ceramic particles and organic binders.